Research Progress on Activation of Persulfate Degradation Wastewater by Molybdenum Compounds AITranslate
Abstract AITranslate
With the development of industrialization,a large number of chemicals are used in daily activities,resulting in more and more refractory organic pollutants in environmental waters,such as pesticides widely used in agriculture,pharmaceuticals employed in the medical industry,dyes and preservatives used in everyday life,even daily necessities such as skin care products and cosmetics. These organic pollutants can enter the environmental water body through various ways and accumulate residues in it and finally enter the human body through direct ingestion,bioaccumulation,and other ways,which pose a great threat to human health. Advanced oxidation technologies (AOPs)are a typical and effective water treatment method. Most AOPs are based on peroxide compounds that can be activated,such as hydrogen peroxide (H2O2),peroxymonosulfate (PMS),peroxydisulfate (PDS),and peracetic acid (PAA)for Fenton/Fenton-like reactions. Advanced oxidation technology using persulfate (PS)as an oxidant (including PMS and PDS)can produce a series of reactive oxygen species (ROS)such as sulfate radical (),hydroxyl radical (·OH),superoxide radical (),and singlet oxygen (1O2)after activation. Compared with H2O2,PS has a higher oxidation potential,a longer half-life,and a wider pH range,which makes PS-based wastewater purification widely concerned. However,the slow activation process and low degradation rate of PS limit its development. As the largest country in molybdenum resources,China has an abundant reserve. The d-orbital electron configuration of molybdenum is flexible,which gives Mo a variety of valence states. Molybdenum-based oxides,molybdenum-based chalcogenides,molybdenum-based carbides,and other molybdenum-based compounds have stable physicochemical properties,good electrical conductivity,flexible valence ability,and excellent photoelectron-hole generation ability via light response. These make them considered good PS activators,and can also be used as cocatalysts in composite catalysts to provide electrons for the reduction of other transition metals,and also have significant advantages in the field of light-assisted activation of PS. In this paper,the mechanism of radical production by PMS,PDS,and H2O2 was analyzed from the structural perspective and compared with the difficulty of their activation to wastewater degradation by structural symmetry. The PS degradation mechanism involved multiple steps,including O-O bond cleavage (activation),free radical generation,and degradation of target pollutants,among which PS activation and free radical generation were the key steps. Focusing on the free radical pathway and non-free radical pathway,the possible PS activation pathways in the degradation process of pollutants were described,and the fundamental differences between the formation modes and degradation mechanisms of both of the above were analyzed by combining valence bond theory and crystal field theory. The paper recommended the existence forms of several molybdenum-based compounds,such as MoO2,MoO3,MoS2 (one trigonal-MoS2,two hexadonal-MoS2,three rhombohedral-MoS2),MoSe2,MoC,and Mo2C,were discussed in detail,and their structural characteristics and corresponding physicochemical properties were discussed in depth. These Mo-based materials have shown significant advantages in many fields,such as transition metal activation and photoactivation. Mo-based materials could not only quickly break the persulfate O-O bond to form and ·OH through the oxidation process,but also reduce the oxidized Mo(Ⅵ)and produce 1O2 to achieve efficient degradation of organic pollutants. At the same time,Mo-based materials could also act as cocatalysts to synergize with other transition metals and participate in pollutant degradation as active and reducing components. Mo-based compounds could also play an important role in the generation of photogenerated electrons under light to assist in the activation of PS. Finally,some problems in the field of molybdenum-based catalysts were pointed out. For example,Mo-based catalysts have shown poor cycling stability in some studies,which was speculated to mean that part of the active sites were occupied by reaction intermediates,resulting in a decrease in the activation ability of PMS. Most of the Mo-based catalysts reported so far remain in the laboratory stage,and their performance in complex actual water bodies was often not ideal,which was far from the purpose of practical application. How to realize the practical application of Mo-based catalysts and then realize the industrial application should be studied.
KeyWords AITranslate
[1]Wang J L, Bai Z Y. Fe-based catalysts for heterogeneous catalytic ozonation of emerging contaminants in water and wastewater[J]. Chemical Engineering Journal, 2017, 312: 79.
[2]Andreozzi R, Caprio V, Insola A, Marotta R. Advanced oxidation processes (AOP) for water purification and recovery[J]. Catalysis Today, 1999, 53(1): 51.
[3]Wang Z, Jiang J, Pang S, Zhou Y, Guan C T, Gao Y, Li J, Yang Y, Qiu W, Jiang C C. Is sulfate radical really generated from peroxydisulfate activated by iron(Ⅱ) for environmental decontamination?[J]. Environmental Science & Technology, 2018, 52(19): 11276.
[4]Dong H, Li Y, Wang S C, Liu W F, Zhou G M, Xie Y F, Guan X H. Both Fe(Ⅳ) and radicals are active oxidants in the Fe(Ⅱ)/peroxydisulfate process[J]. Environmental Science & Technology Letters, 2020, 7(3): 219.
[5]Zhang L L, Zhou X F, Yang L B, Xu Y, Liu T C, Ji R C, Yang Y C, Zhang Y L, Chen J B. Boosting peracetic acid activation with Cu single-atom catalysts for sulfamethoxazole abatement: a nonradical pathway and 'double engine' driving mechanism[J]. Applied Catalysis B: Environment and Energy, 2024, 349: 123897.
[6]Wang S Z, Wang J L. Activation of peroxymonosulfate by sludge-derived biochar for the degradation of triclosan in water and wastewater[J]. Chemical Engineering Journal, 2019, 356: 350.
[7]de Souza P A L, Camacho F G, de Almeida da Silva I R, Gonçalves F F, Benincá C, Zanoelo E F. An experimental and modeling study of the chain initiation reaction in heterogeneous Fenton systems with zero valent iron[J]. Chemical Engineering Journal, 2020, 393: 124665.
[8]Wang J L, Wang S Z. Activation of persulfate (PS) and peroxymonosulfate (PMS) and application for the degradation of emerging contaminants[J]. Chemical Engineering Journal, 2018, 334: 1502.
[9]Li Y K, Zhang D, Chen Q S, Chao C, Sun J H, Dong S Y, Sun Y Y. Synthesis of rGO/g-C3N4 for methyl orange degradation in activating peroxydisulfate under simulated solar light irradiation[J]. Journal of Alloys and Compounds, 2022, 907: 164500.
[10](任冬梅, 王星稳, 冷春鹏, 韩超, 孟伟. 基于双金属有机骨架的Cu/Cu2O/C制备及其在对乙酰氨基酚测定中的应用[J]. 分析试验室, 2023, 42(9): 1144.)
D M Ren, X W Wang, C P Leng, C Han, W Meng. Preparation of Cu/Cu2O/C based on bimetallic organic frameworks and its application in the determination of acetaminophen[J]. Chinese Journal of Analysis Laboratory, 2023, 42(9): 1144.
[11]Huang Z Y, Wu P X, Liu C H, Chen M Q, Yang S S, Dang Z, Zhu N W. Multiple catalytic reaction sites induced non-radical/radical pathway with graphene layers encapsulated Fe-N-C toward highly efficient peroxymonosulfate (PMS) activation[J]. Chemical Engineering Journal, 2021, 413: 127507.
[12]Dong H Y, Xu Q H, Lian L S, Li Y, Wang S C, Li C, Guan X H. Degradation of organic contaminants in the Fe(Ⅱ)/peroxymonosulfate process under acidic conditions: the overlooked rapid oxidation stage[J]. Environmental Science & Technology, 2021, 55(22): 15390.
[13]Wang W X, Xiong F Y, Zhu S H, Chen J H, Xie J, An Q Y. Defect engineering in molybdenum-based electrode materials for energy storage[J]. eScience, 2022, 2(3): 278.
[14]Gu Y, Wu A P, Jiao Y Q, Zheng H R, Wang X Q, Xie Y, Wang L, Tian C G, Fu H G. Two-dimensional porous molybdenum phosphide/nitride heterojunction nanosheets for pH-universal hydrogen evolution reaction[J]. Angewandte Chemie, 2021, 133(12): 6747.
[15]Ren H Q, Sun S D, Cui J, Li X F. Synthesis, functional modifications, and diversified applications of molybdenum oxides micro-/nanocrystals: a review[J]. Crystal Growth & Design, 2018, 18(10): 6326.
[16]Zhao T B, Lan D, Jia Z R, Gao Z G, Wu G L. Hierarchical porous molybdenum carbide synergic morphological engineering towards broad multi-band tunable microwave absorption[J]. Nano Research, 2024, 17(11): 9845.
[17](彭银利, 张柳英, 李梅, 闫基森, 张玺, 解芳. 不同凝固条件下Fe-Sn合金的组织形貌及相组成[J]. 有色金属工程, 2024, 14(7): 43.)
Y L Peng, L Y Zhang, M Li, J S Yan, X Zhang, F Xie. Microstructure and phase constitution of Fe-Sn alloy under different solidification conditions[J]. Nonferrous Metals Engineering, 2024, 14(7): 43.
[18]Du X Z, Li R T, Xin H, Fan Y M, Liu C X, Feng X H, Wang J Y, Dong C, Wang C, Li D, Fu Q, Bao X H. In-situ dynamic carburization of Mo oxide with unprecedented high CO formation rate in reverse water-gas shift reaction[J]. ACS Catalysis, 2024, 63: e202411761.
[19](李豪, 赵凤, 沈忱思. Cu0-Fe3O4@壳聚糖微球的制备及其对染料污染物的催化氧化[J]. 分析试验室, 2024, 43(3): 335.)
H Li, F Zhao, C S Shen. Preparation of Cu0-Fe3O4@chitosan microspheres and its catalytic oxidation of dye contaminants[J]. Chinese Journal of Analysis Laboratory, 2024, 43(3): 335.
[20]Zhao Z Y, Wang P F, Song C L, Zhang T, Zhan S H, Li Y. Enhanced interfacial electron transfer by asymmetric Cu‐Ov‐in sites on In2O3 for efficient peroxymonosulfate activation[J]. Angewandte Chemie International Edition, 2023, 62(11): e202216403.
[21]Song X Y, Shi Y, Wu Z L, Huang B K, Wang X H, Zhang H, Zhou P, Liu W, Pan Z C, Xiong Z K, Lai B. Unraveling the discriminative mechanisms for peroxy activation via atomically dispersed Fe-N5 sites for tunable water decontamination[J]. Applied Catalysis B: Environmental, 2024, 340: 123240.
[22](江训金, 黄国泉, 张锋, 李晨, 史翔辉, 祝斌. 工业废水深度除镉技术研究与工程应用[J]. 铜业工程, 2024, (6): 107.)
X J Jiang, G Q Huang, F Zhang, C Li, X H Shi, B Zhu. Research and engineering application of depth removal technology of cadmium for industrial wastewater[J]. Copper Engineering, 2024, (6): 107.
[23]Huang W Q, Xiao S, Zhong H, Yan M, Yang X. Activation of persulfates by carbonaceous materials: a review[J]. Chemical Engineering Journal, 2021, 418: 129297.
[24]Fang Q Z, Yang H L, Ye S J, Zhang P, Dai M Y, Hu X J, Gu Y L, Tan X F. Generation and identification of 1O2 in catalysts/peroxymonosulfate systems for water purification[J]. Water Research, 2023, 245: 120614.
[25]Xu W B, Huang D L, Wang G F, Zhou W, Du L, Xiao R H, Li R J, Huang H, Lei Y. Generation, function and identification of O2·− in persulfate-based advanced oxidation process for pollutants degradation[J]. Chemical Engineering Journal, 2024, 499: 156245.
[26]Kohantorabi M, Moussavi G, Giannakis S. A review of the innovations in metal-and carbon-based catalysts explored for heterogeneous peroxymonosulfate (PMS) activation, with focus on radical vs. non-radical degradation pathways of organic contaminants[J]. Chemical Engineering Journal, 2021, 411: 127957.
[27]Hazarika K K, Goswami C, Bharali P. Removal of persistent organic pollutants using redox active metal oxide nanocatalysts via advanced oxidation process[J]. Environmental chemistry for a sustainable world, 2022, 69: 215.
[28]Wu C H, Dong C D, Chen C W, Lin Y L. Mineralization of sulfamethoxazole by ozone-based and Fenton/Fenton-like-based processes[J]. Reaction Kinetics, Mechanisms and Catalysis, 2022, 135(1): 441.
[29]Xiang T, Yang J J, Shi L Y, Li L, Chen Q Y, Zhou J. Defective MoSe2 for enhanced remediation of 2, 4-D by boosting peroxymonosulfate activation[J]. Journal of Environmental Chemical Engineering, 2024, 12(5): 113418.
[30]Inzani K, Nematollahi M, Vullum-Bruer F, Grande T, Reenaas T W, Selbach S M. Electronic properties of reduced molybdenum oxides[J]. Physical Chemistry Chemical Physics, 2017, 19(13): 9232.
[31](王浦璠, 邓道繁, 陈果, 张慧宁, 廖春发. 基于第一性原理的Fe(111)/Al2O3(0001)界面稳定性研究[J]. 有色金属科学与工程, 2024, 15(2): 158.)
P F Wang, D F Deng, G Chen, H N Zhang, C F Liao. Stability of Fe(111)/Al2O3(0001) interface based on first principles[J]. Nonferrous Metals Science and Engineering, 2024, 15(2): 158.
[32]Chen X, Vione D, Borch T, Wang J, Gao Y Z. Nano-MoO2 activates peroxymonosulfate for the degradation of PAH derivatives[J]. Water Research, 2021, 192: 116834.
[33]Ji J, Aleisa R M, Duan H, Zhang J L, Yin Y D, Xing M Y. Metallic active sites on MoO2(110) surface to catalyze advanced oxidation processes for efficient pollutant removal[J]. iScience, 2020, 23(2): 100861.
[34]Alnaggar G, Hezam A, Bajiri M A, Drmosh D A, Ananda S. Sulfate radicals induced from peroxymonosulfate on electrochemically synthesized TiO2-MoO3 heterostructure with Ti–O–Mo bond charge transfer pathway for potential organic pollutant removal under solar light irradiation[J]. Chemosphere, 2022, 303: 134562.
[35]Yuan Y, Guo R T, Hong L F, Ji X Y, Li Z S, Lin Z D, Pan W G. Recent advances and perspectives of MoS2-based materials for photocatalytic dyes degradation: a review[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 611: 125836.
[36]Hasija V, Raizada P, Thakur V K, Khan A A P, Asiri A M, Singh P. An overview of strategies for enhancement in photocatalytic oxidative ability of MoS2 for water purification[J]. Journal of Environmental Chemical Engineering, 2020, 8(5): 104307.
[37]Du M M, Yi Q Y, Ji J H, Zhu Q H, Duan H, Xing M Y, Zhang J L. Sustainable activation of peroxymonosulfate by the Mo(Ⅳ) in MoS2 for the remediation of aromatic organic pollutants[J]. Chinese Chemical Letters, 2020, 31(10): 2803.
[38]Li X G, Guo Y X, Yan L G, Yan T, Song W, Feng R, Zhao Y W. Enhanced activation of peroxymonosulfate by Peroxydisulfate activation MoS2 for degradation of tetracycline: boosting molybdenum activity by sulfur vacancies[J]. Chemical Engineering Journal, 2022, 429: 132234.
[39]Sun Y B, Li R P, Song C L, Zhang H, Cheng Y C, Nie A, Li H C, Dionysios D D, Qian J S, Pan B C. Origin of the improved reactivity of MoS2 single crystal by confining lattice Fe atom in peroxymonosulfate-based Fenton-like reaction[J]. Applied Catalysis B: Environmental, 2021, 298: 120537.
[40]Lu J, Zhou Y, Zhou Y B. Efficiently activate peroxymonosulfate by Fe3O4@MoS2 for rapid degradation of sulfonamides[J]. Chemical Engineering Journal, 2021, 422: 130126.
[41]Yang J H, Sun J L, Chen S, Lan D Q, Li Z H, Li Z J, Wei J W, Yu Z B, Zhu H X, Wang S F, Hou Y P. S-scheme 1T phase MoSe2/AgBr heterojunction toward antibiotic degradation: photocatalytic mechanism, degradation pathways, and intermediates toxicity evaluation[J]. Separation and Purification Technology, 2022, 290: 120881.
[42]Wang Y, Zhao J X, Chen Z, Zhang F, Guo W, Lin H M, Qu F Y. Construction of Z-scheme MoSe2/CdSe hollow nanostructure with enhanced full spectrum photocatalytic activity[J]. Applied Catalysis B: Environmental, 2019, 244: 76.
[43]Li L, Zeng H, Tang R D, Zhou Z Q, Xiong S, Li W B, Huang Y, Deng Y C. Carbon nitride with grafted molecular as electron acceptor and active site to achieve efficient photo-activated peroxymonosulfate for organic pollutants removal[J]. Applied Catalysis B: Environmental, 2024, 345: 123693.
[44]Dong C C, Wang Z Q, Ye Z C, He J H, Zheng Z X, Gong X Q, Zhang J L, Lo I M C. Superoxide radicals dominated visible light driven peroxymonosulfate activation using molybdenum selenide (MoSe2) for boosting catalytic degradation of pharmaceuticals and personal care products[J]. Applied Catalysis B: Environmental, 2021, 296: 120223.
[45]Yang J J, Guo B Y, Li L, Chen Q Y, Shen C S, Zhou J. Enhancement of peroxymonosulfate activation for 2, 4-dichlorophenoxyacetic acid removal by MoSe2 induced Fe redox cycles[J]. Chemosphere, 2023, 311: 137170.
[46]Dong C C, Bao Y, Xing M Y, Anpo M, Zhang J L. Dual-functional Mo2C quantum dots enriched N-doped graphitic carbon layers in advanced oxidation processes (AOPs)[J]. Applied Catalysis A: General, 2023, 649: 118963.
[47]Zhu E, Yuan D L, Wang Z L, Wang Z B, Zhang Q R, Tang S F. Insight into the activation mechanism of peracetic acid by molybdenum carbide for sulfamethoxazole decomposition[J]. Chemical Engineering Journal, 2023, 474: 145824.
[48]Ma Y F, Guan G Q, Hao X G, Cao J, Abudula A. Molybdenum carbide as alternative catalyst for hydrogen production–a review[J]. Renewable and Sustainable Energy Reviews, 2017, 75: 1101.
[49]Lin L L, Zhou W, Gao R, Yao S Y, Zhang X, Xu W Q, Zheng S J, Jiang Z, Yu Q L. Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts[J]. Nature, 2017, 544(7648): 80.
[50]Yao S Y, Zhang X, Zhou W, Gao R, Xu W Q, Ye Y F, Lin L L, Wen X D, Liu P, Chen B B, Crumlin E, Guo J H, Zuo Z J, Li W Z, Xie J L, Lu L, Kiely C J, Gu L, Shi C, Rodriguez J, Ma D. Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water-gas shift reaction[J]. Science, 2017, 357(6349): 389.
[51]Dong C C, Bao Y, Xing M Y, Anpo M, Zhang J L. Dual-functional Mo2C quantum dots enriched N-doped graphitic carbon layers in advanced oxidation processes (AOPs)[J]. Applied Catalysis A: General, 2023, 649: 118963.
[52]Yang L, Chen H, Jia F F, Peng W J, Tian X, Xia L, Wu X Y, Song S X. Emerging hexagonal Mo2C nanosheet with (002) facet exposure and Cu incorporation for peroxymonosulfate activation toward antibiotic degradation[J]. ACS Appl. Mater. Interfaces, 2021, 13 (12), 14342.
[53]Chen X, Gudda F O, Hu X J, Waigi M G, Gao Y Z. Degradation of bisphenol A in an oxidation system constructed from Mo2C MXene and peroxymonosulfate[J]. Npj Clean Water, 2022, 5(1): 66.
[54]Chen X, Wang M, Liu J Z, Liu C Y, Chen Y F. Enhancing sulfamerazine degradation via peroxymonosulfate with Fe-doped Mo2C materials: catalytic performance and mechanistic insights[J]. Journal of Environmental Chemical Engineering, 2024, 12(6): 114622.
[55]Lian Z, Wu T, Zhang X N, Cai S F, Xiong Y L, Yang R. Synergistic degradation of tetracycline from Mo2C/MoO films mediated peroxymonosulfate activation and visible-light triggered photocatalysis[J]. Chemical Engineering Journal, 2023, 469: 143774.
[56]Dong C C, Bao Y, Xing M Y, Anpo M, Zhang J L. Dual-functional Mo2C quantum dots enriched N-doped graphitic carbon layers in advanced oxidation processes (AOPs)[J]. Applied Catalysis A: General, 2023, 649: 118963.
[57]Tišler Z, Velvarská R, Skuhrovcová L, Pelíšková L, Akhmetzyanova U. Key role of precursor nature in phase composition of supported molybdenum carbides and nitrides[J]. Materials, 2019, 12(3): 415.
[58]Jyothirmayee Aravind S S, Ramanujachary K, Mugweru A, Vaden T D. Molybdenum phosphide-graphite nanomaterials for efficient electrocatalytic hydrogen production[J]. Applied Catalysis A: General, 2015, 490: 101.
[59]He W T, Huang L P, Wang X Y, Zhang J. Molybdenum nitride(γ-Mo2N) as a novel co-catalyst to enhance Fe(Ⅲ)/Fe(Ⅱ) cycle for homogeneous and heterogeneous peroxymonosulfate activation: performance and mechanism[J]. Journal of Environmental Chemical Engineering, 2024, 12(2): 112404.
[60]Chen X, Chen Y F, Li S R, Xue C, Liu D F, Huang W L. Unraveling the crucial role of Mo2N from Fe/Mo bimetal MOF-derived catalyst in initiating Fe3+/Fe2+ redox cycle to activate peroxymonosulfate for dibutyl phthalate degradation[J]. Chemical Engineering Journal, 2023, 476: 146693.
[61]Li X Y, Huang S Q, Xu H H, Deng Y P, Wang Z, Liu Z Q. Molybdenum phosphide (MoP) with dual active sites for the degradation of diclofenac in Fenton-like system[J]. Chinese Chemical Letters, 2022, 33(3): 1321.
[62]Xiang S X, Dong H R, Li Y J, Xiao J Y, Dong Q X, Hou X Z. Novel flower-like Fe-Mo composite for peroxydisulfate activation toward efficient degradation of carbamazepine[J]. Separation and Purification Technology, 2023, 305: 122487.
[63]Yao Y Y, Zhao W Y, Zhao X Y, Liu C Q, Chen Z W, Xiao C M, Zhu Z G, Yang Y, Zhou Y J, Qi J W, Li J S. Fit-for-purpose upcycle of wastewater sludge into Fe-S-Mo catalyst for simultaneous resource recovery and water decontamination[J]. Applied Catalysis B: Environment and Energy, 2025, 365: 124969.
[64]Liu Z, Su R D, Xu F, Xu X, Gao B Y, Li Q. The unique Fe3Mo3N structure bestowed efficient Fenton‐like performance of the iron‐based catalysts: the double enhancement of radicals and nonradicals[J]. Advanced Materials, 2024, 36(18): 2311869.
[65]Fan Y H, Li Y Q, Hayat F, Liu C, Li J, Chen M. Multi-targeted removal of coexisted antibiotics in water by the synergies of radical and non-radical pathways in PMS activation[J]. Separation and Purification Technology, 2023, 305: 122475.
Basic Information:
DOI:10.13373/j.cnki.cjrm.XY24120021
Chinese Library Classification Number:X703
Citation Information:
With the development of industrialization,a large number of chemicals are used in daily activities,resulting in more and more refractory organic pollutants in environmental waters,such as pesticides widely used in agriculture,pharmaceuticals employed in the medical industry,dyes and preservatives used in everyday life,even daily necessities such as skin care products and cosmetics. These organic pollutants can enter the environmental water body through various ways and accumulate residues in it and finally enter the human body through direct ingestion,bioaccumulation,and other ways,which pose a great threat to human health. Advanced oxidation technologies (AOPs)are a typical and effective water treatment method. Most AOPs are based on peroxide compounds that can be activated,such as hydrogen peroxide (H2O2),peroxymonosulfate (PMS),peroxydisulfate (PDS),and peracetic acid (PAA)for Fenton/Fenton-like reactions. Advanced oxidation technology using persulfate (PS)as an oxidant (including PMS and PDS)can produce a series of reactive oxygen species (ROS)such as sulfate radical (),hydroxyl radical (·OH),superoxide radical (),and singlet oxygen (1O2)after activation. Compared with H2O2,PS has a higher oxidation potential,a longer half-life,and a wider pH range,which makes PS-based wastewater purification widely concerned. However,the slow activation process and low degradation rate of PS limit its development. As the largest country in molybdenum resources,China has an abundant reserve. The d-orbital electron configuration of molybdenum is flexible,which gives Mo a variety of valence states. Molybdenum-based oxides,molybdenum-based chalcogenides,molybdenum-based carbides,and other molybdenum-based compounds have stable physicochemical properties,good electrical conductivity,flexible valence ability,and excellent photoelectron-hole generation ability via light response. These make them considered good PS activators,and can also be used as cocatalysts in composite catalysts to provide electrons for the reduction of other transition metals,and also have significant advantages in the field of light-assisted activation of PS. In this paper,the mechanism of radical production by PMS,PDS,and H2O2 was analyzed from the structural perspective and compared with the difficulty of their activation to wastewater degradation by structural symmetry. The PS degradation mechanism involved multiple steps,including O-O bond cleavage (activation),free radical generation,and degradation of target pollutants,among which PS activation and free radical generation were the key steps. Focusing on the free radical pathway and non-free radical pathway,the possible PS activation pathways in the degradation process of pollutants were described,and the fundamental differences between the formation modes and degradation mechanisms of both of the above were analyzed by combining valence bond theory and crystal field theory. The paper recommended the existence forms of several molybdenum-based compounds,such as MoO2,MoO3,MoS2 (one trigonal-MoS2,two hexadonal-MoS2,three rhombohedral-MoS2),MoSe2,MoC,and Mo2C,were discussed in detail,and their structural characteristics and corresponding physicochemical properties were discussed in depth. These Mo-based materials have shown significant advantages in many fields,such as transition metal activation and photoactivation. Mo-based materials could not only quickly break the persulfate O-O bond to form and ·OH through the oxidation process,but also reduce the oxidized Mo(Ⅵ)and produce 1O2 to achieve efficient degradation of organic pollutants. At the same time,Mo-based materials could also act as cocatalysts to synergize with other transition metals and participate in pollutant degradation as active and reducing components. Mo-based compounds could also play an important role in the generation of photogenerated electrons under light to assist in the activation of PS. Finally,some problems in the field of molybdenum-based catalysts were pointed out. For example,Mo-based catalysts have shown poor cycling stability in some studies,which was speculated to mean that part of the active sites were occupied by reaction intermediates,resulting in a decrease in the activation ability of PMS. Most of the Mo-based catalysts reported so far remain in the laboratory stage,and their performance in complex actual water bodies was often not ideal,which was far from the purpose of practical application. How to realize the practical application of Mo-based catalysts and then realize the industrial application should be studied.
quote
| GB/T 7714-2015 | [1] Yitong Yang, Qiaoyun Chen, Mengjia Li, et al. Research Progress on Activation of Persulfate Degradation Wastewater by Molybdenum Compounds[J]. Chinese Journal of Rare Metals, 2025, 49(9): 1454-1465. DOI:10.13373/j.cnki.cjrm.XY24120021. |
| MLA | [1] Yitong Yang, et al., "Research Progress on Activation of Persulfate Degradation Wastewater by Molybdenum Compounds." Chinese Journal of Rare Metals, vol. 49, no. 9, 2025, pp. 1454-1465, https://doi.org/10.13373/j.cnki.cjrm.XY24120021. |
| APA | [1] Yitong Yang, Qiaoyun Chen, Mengjia Li, Li Song, Kemei Pei, & Lei Li. (2025). Research Progress on Activation of Persulfate Degradation Wastewater by Molybdenum Compounds. Chinese Journal of Rare Metals, 49(9), 1454-1465. https://doi.org/10.13373/j.cnki.cjrm.XY24120021 |
| IEEE | [1] Yitong Yang, Qiaoyun Chen, Mengjia Li, Li Song, Kemei Pei, and Lei Li, "Research Progress on Activation of Persulfate Degradation Wastewater by Molybdenum Compounds," Chinese Journal of Rare Metals, vol. 49, no. 9, pp. 1454-1465, 2025, doi: 10.13373/j.cnki.cjrm.XY24120021. keywords: {molybdenum-based compounds;persulfate (PS);advanced oxidation techniques (AOPs);water treatment;organic pollutants} |
